Acid disazo dyes as well as sulphonamides as their intermediate product

ABSTRACT

Disazo dyes of formula (I) where one of the two symbols X 1  and X 2  means hydroxy and the other amino and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are as defined in the specification. The invention also relates to sulphonamides as their intermediate products and to the use of the dyes for the dyeing of natural and synthetic substrates.

This application is a 371 of PCT/EP97/00174 filed Jan. 16, 1997.

The present invention relates to novel disazo dyes of the formula I ##STR2## where one of the two radicals X¹ and X² is hydroxyl and the other is amino,

R¹ is hydrogen, hydroxysulfonyl or a radical of the formula CO--Ar, CO--Alk, SO₂ --Ar, SO₂ --Alk, SO₂ --OAr, ##STR3## R² is hydrogen or R² and R¹ together are a radical of the formula

    CO--NZ.sup.1 --CO

    or ##STR4## R.sup.3 is hydrogen, hydroxysulfonyl, C.sub.1 -C.sub.4 -alkyl, halogen or a radical of the formula SO.sub.2 --OAr, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr or R.sup.3 and R.sup.2 together are a radical of the formula CO--NZ.sup.1 --Y,

R⁴ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAlk, CO--NHAr, CO--N(Ar)Alk, CO--N(Alk)₂, SO₂ --Alk, SO₂ --OAr, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk or SO₂ --NHAr,

R⁵ is hydrogen, C₁ -C₄ -alkyl, halogen or hydroxysulfonyl, and

R⁶, R⁷ and R⁸ are each independently of the others hydrogen, C₁ -C₄ -alkyl, halogen, cyano, nitro, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAr, CO--OAlk, CO--N(Ar)Alk, CO--N(Alk)₂, SO₂ --Ar, SO₂ --Alk, SO₂ --CH₂ CH═CH₂, SO₂ --CH═CH₂, SO₂ --C₂ H₄ --Q, SO₂ --OAr, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk, SO₂ --NHAr, ##STR5## where Alk is C₁ -C₈ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenoxy, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl,

Ar is phenyl or naphthyl, and each of these radicals may be substituted by C₁ -C₄ -alkyl, phenyl-(C₁ -C₄)-alkyl, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-(C₁ -C₄)-alkyl, phenoxy, hydroxyl, carboxyl, C₁ -C₄ -alkanoylamino with or without interruption by 1 oxygen atom in ether function in the alkyl chain, benzoylamino, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO₂ --Alk, SO₂ --CH₂ CH═CH₂, SO₂ --CH═CH₂, SO₂ --C₂ H₄ --Q, SO₂ --NHAlk, SO₂ --N(Alk)₂, SO₂ --G, SO₂ --OG, SO₂ --NHG or SO₂ --N(Alk)G,

Y is methylene or carbonyl,

Z¹ is hydrogen or a radical of the formula Alk or Ar,

Z² is hydrogen or hydroxysulfonyl,

Q is hydroxyl or an alkali-detachable group, and

G is phenyl which may be substituted by C₁ -C₄ -alkyl, carboxyl, hydroxysulfonyl or C₁ -C₄ -alkanoylamino or is naphthyl which may be substituted by hydroxysulfonyl,

and at least one of the radicals R¹, R², R³, R⁴ or R⁵ and at least one of the radicals R⁶, R⁷ or R⁸ are not hydrogen,

sulfonamides as their intermediates and also the use of the novel dyes for dyeing natural or synthetic substrates.

It is an object of the present invention to provide novel disazo-based acid dyes having advantageous application properties.

We have found that this object is achieved by the acid disazo dyes of the formula I defined at the beginning.

If R³ and R² together are a radical of the formula CO--NZ¹ --Y, this radical can be bonded to the ring positions of R² and R³ via Y or CO, or vice versa.

Any alkyl appearing in the abovementioned formula I may be straight-chain or branched.

Any substituted alkyl appearing in the abovementioned formula generally contains 1 or 2 substituents.

Any alkyl appearing in the abovementioned formulae with interruption by oxygen atoms in ether function is preferably alkyl interrupted by 1 or 2 oxygen atoms in ether function.

Any substituted phenyl appearing in the abovementioned formulae generally contains from 1 to 3 substituents.

R³, R⁵, R⁶, R⁷, R⁸ and Alk are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, fluorine, chlorine or bromine.

Alk may also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl (the above designation isooctyl is a trivial name derived from the oxo process alcohols--cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 1, pages 290 to 293, and Vol. A 10, pages 284 and 285), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2- or 4-methylthiobutyl, 2- or 4-ethylthiobutyl, 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2- or 3-methylsulfonylpropyl, 2- or 3-ethylsulfonylpropyl, 2- or 4-methylsulfonylbutyl, 2- or 4-ethylsulfonylbutyl, chloromethyl, 2-chloroethyl, 2- or 3-chloropropyl, benzyl, 1- or 2-phenylethyl, 2-, 3- or 4-hydroxysulfonylbenzyl, 2-(2-,3- or 4-hydroxysulfonylphenyl)ethyl, 3-benzyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2- or 3-cyanopropyl, carbamoylmethyl, 2-carbamoylethyl, 2- or 3-carbamoylpropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, carboxylmethyl, 2-carboxylethyl, 2- or 3-carboxylpropyl, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2-sulfatoethyl or 2- or 3-sulfatopropyl.

Ar may also be for example phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-phenoxyphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-formylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or 4-propionylaminophenyl, 2-, 3- or 4-methoxyacetylaminophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-carboxyphenyl or 2-, 3- or 4-hydroxysulfonylphenyl, 2-, 3- or 4-benzoylaminophenyl, 2-, 3- or 4-pyrrolidinylsulfonylphenyl, 2-, 3- or 4-piperidinesulfonylphenyl, 2-, 3- or 4-morpholinylsulfonylphenyl, 2-, 3- or 4-methylsulfonylphenyl, 2-, 3- or 4-carboxymethylsulfonylphenyl, 2-, 3- or 4-vinylsulfonylphenyl, 2-, 3- or 4-(2-hydroxyethyl)sulfonylphenyl, 2-, 3- or 4-(2-sulfatoethyl)sulfonylphenyl, 2-, 3- or 4-ethylsulfamoylphenyl, 2-, 3- or 4-(2-hydroxyethyl)sulfamoylphenyl, 2-, 3- or 4-bis(2-hydroxyethyl)sulfamoylphenyl, naphth-1-yl, naphth-2-yl, 2-hydroxysulfonylnaphth-1-yl, 5-hydroxysulfonylnaphth-1-yl or 5-hydroxysulfonylnaphth-2-yl.

Z¹ is, as Alk may also be, for example cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Q is hydroxyl or an alkali-detachable group. Such groups are for example chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, OSO₃ H, SSO₃ H, OP(O) (OH)₂, C₁ -C₄ -alkylsulfonyloxy, phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino, cyanoamino or a radical of the formula ##STR6## where W¹, W² and W³ are each independently of the others C₁ -C₄ -alkyl or benzyl and An.sup.⊖ is in each case one equivalent of an anion. Suitable anions include for example fluoride, chloride, bromide, iodide, mono-, di- and trichloroacetate, methylsulfonate, phenylsulfonate or 2- or 4-methylphenylsulfonate.

R¹ and R⁴ are each for example benzoyl, 2-, 3- or 4-methylbenzoyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylbenzoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or butylsulfonyl.

R¹ may also be for example 5-methyl-, 5-ethyl-, 5-propyl-, 5-butyl- or 5-phenyl-1,3,4-oxadiazol-2-yl, 3-methyl-, 3-ethyl-, 3-propyl-, 3-butyl- or 3-phenyl-1,2,4-oxadiazol-5-yl, phenylsulfonyl, 2-, 3- or 4-methylphenylsulfonyl or 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenylsulfonyl.

R³, R⁶, R⁷ and R⁸ are, as R¹ and R⁴ may also be, for example phenoxysulfonyl or 2-, 3- or 4-methylphenoxysulfonyl.

R³, R⁴, R⁶, R⁷ and R⁸ may each also be for example N-phenyl-N-methylsulfamoyl, N-phenyl-N-ethylsulfamoyl, N-phenyl-N-propylsulfamoyl, N-phenyl-N-butylsulfamoyl, phenylsulfamoyl or 2-, 3- or 4-methylphenylsulfamoyl.

R⁴, R⁶, R⁷ and R⁸ may each also be for example dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, bis(2-hydroxyethyl)sulfamoyl, bis(carboxymethyl)sulfamoyl, bis(2-carboxyethyl)sulfamoyl, methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, 2-hydroxyethylsulfamoyl, carboxymethylsulfamoyl or 2-carboxyethylsulfamoyl.

R⁴, R⁶, R⁷ and R⁸ may each also be for example dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, bis(2-hydroxyethyl)carbamoyl, bis(carboxymethyl)carbamoyl, bis(2-carboxyethyl)carbamoyl, N-phenyl-N-methylcarbamoyl, N-phenyl-N-ethylcarbamoyl, N-phenyl-N-propylcarbamoyl or N-phenyl-N-butylcarbamoyl.

R⁴ may also be for example methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, 2-hydroxyethylcarbamoyl, carboxymethylcarbamoyl or 2-carboxyethylcarbamoyl.

R⁶, R⁷ and R⁸ may each also be for example 2-hydroxyethylsulfonyl, 2-chloroethylsulfonyl, 2-sulfatoethylsulfonyl or 2-acetyloxyethylsulfonyl.

The radicals ##STR7## conform for example to the formulae ##STR8##

Since the disazo dyes of the formula I contain a plurality of hydroxysulfonyl groups and optionally also carboxyl groups, their salts are likewise encompassed by the invention.

Suitable salts are metal or ammonium salts. Metal salts are in particular the lithium, sodium or potassium salts. Ammonium salts for the purposes of the present invention are those salts with either unsubstituted or substituted ammonium cations. Substituted ammonium cations are for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations or those cations derived from nitrogenous five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl is here in general to be understood as meaning straight-chain or branched C₁ -C₂₀ -alkyl which may be substituted by from 1 to 3 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms in ether function.

Preference is given to disazo dyes of the formula I containing 3, 4 or 5, in particular 3 or 4, hydroxysulfonyl groups.

Preference is further given to disazo dyes of the formula I containing 1 or 2 carboxyl groups.

Preference is further given to disazo dyes of the formula I containing 2 hydroxysulfonyl groups, 2 hydroxyl groups and optionally 1 carboxyl group.

Preference is further given to disazo dyes of the formula I where Alk is C₁ -C₆ -alkyl which may be interrupted by 1 or 2 oxygen atoms in ether function or by 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, sulfato, chlorine, cyano, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl.

Preference is further given to disazo dyes of the formula I where Ar is phenyl which may be substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, carboxyl, C₁ -C₄ -alkanoylamino, methoxyacetylamino, hydroxysulfonyl or a radical of the formula SO₂ --CH═CH₂, SO₂ --C₂ H₄ --Q, SO₂ --NHAlk, SO₂ --N(Alk)₂, SO₂ --G, SO₂ --OG, SO₂ --NHG or SO₂ --N(Alk)G.

Preference is further given to disazo dyes of the formula II ##STR9## where R⁹ is a radical of the formula SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂, SO₂ --C₂ H₄ Q, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholidinylsulfonyl or a radical of the formula SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk or SO₂ --NHAr,

R¹, R², R³, R⁴, R⁵, X¹ and X² are each as defined above, and R⁹ is in the 3- or 4-position.

Particular preference is given to disazo dyes containing a radical of the formula SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂ or SO₂ --C₂ H₄ --Q, especially those dyes which contain a radical of the formula SO₂ --C₂ H₄ --Q¹, where Q¹ is an alkali-detachable group.

Emphasis is given to dyes of the general formula III ##STR10## where R¹⁰ is a radical of the formula SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂ or SO₂ --C₂ H₄ --Q,

R¹, R², R³, R⁴, R⁵, X¹ and X² are each as defined above, and R¹⁰ is in the 3- or preferably 4-position.

Particular preference is further given to disazo dyes of the formula I where R⁶, R⁷ or R⁸ is a radical of the formula SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk, SO₂ --NHAr or pyrrolidinylsulfonyl, piperidinylsulfonyl or morpholinylsulfonyl. Disazo dyes of the formula I where R³ and/or R⁷ is a radical of the formula SO₂ --N(Ar)Alk or SO₂ --NHAr are of particular importance. Emphasis is given to the dyes of the general formulae IV and V ##STR11## where R¹, R², R³, R⁴, R⁵ R⁶, R⁷, R⁸, X¹, X², Alk and Ar are each as defined above and the sulfonamide group is in the 3-position or preferably in the 4-position.

Particular preference is given to dyes of the formula I where R³ and/or R⁷ are each a radical of the formula SO₂ --N(Ar)Alk, where Ar contains a radical of the formula SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂ or SO₂ --CH₂ CH═CH₂. Preference is further given to dyes of the formulae IV and V where Ar is a phenyl or naphthyl group which is substituted by a radical of the formula SO₂ --CH₂ --CH₂ --Q, SO₂ --CH═CH₂ or SO₂ --CH₂ --CH═CH₂. Emphasis is given in particular to dyes of the formula IVa ##STR12## where R¹, R², R³, R⁴ and R⁵ are each as defined above, the ring A may be benzofused,

Alk is C₁ -C₈ -alkyl with or without interruption by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and with or without substitution by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl,

U¹ is hydrogen, C₁ -C₄ -alkyl, unsubstituted or C₁ -C₄ -alkoxy- or phenyl-substituted, or halogen, and

U² is a radical of the formula SO₂ --CH═CH₂ or SO₂ --C₂ H₄ --Q, where Q is hydroxyl or an alkali-detachable group,

and the sulfonamide radical is in the 3- or 4-position.

Particular preference is further given to dyes of the formula IVb ##STR13## where R¹, R², R³, R⁴ and R⁵ are each as defined above, the ring A¹ may be benzofused and may be substituted by hydroxysulfonyl, carboxyl, C₁ -C₄ -alkyl, chlorine or C₁ -C₄ -alkoxy,

Alk is C₁ -C₈ -alkyl with or without interruption by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and with or without substitution by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl,

and the sulfonamide radical is in the 3- or 4-position. Preference is given especially to dyes of formula IVb where the ring A is mono- or disubstituted by carboxyl or hydroxysulfonyl.

Preference is further given to disazo dyes of the formulae Ia to In ##STR14## where T¹ is Alk or Ar, T² is hydrogen or hydroxysulfonyl, and X¹, X², R³, R⁴, R⁶, R⁷, R⁸, Y, Z¹, Alk and Ar are each as defined above.

Preference is further given to disazo dyes of the formulae I and also Ia to In where R⁶ and R⁸ are each hydrogen and R⁷ is a radical R⁹ which is as defined above, and in particular a radical of the formula SO₂ --N(Ar)Alk, where Ar and Alk are each as defined above.

Preference is further given to disazo dyes of the formulae I and also Ia to In containing a radical of the formula SO₂ --CH═CH₂ or in particular SO₂ --C₂ H₄ --Q where Q is as given above and denotes in particular sulfato, chlorine or acetyloxy.

Preference is further given to disazo dyes of the formula I where R¹, R⁶, R⁷ or R⁸ is an oxadiazole radical and especially of the formulae II, III, IV, IVa and IVb where R¹ is an oxadiazole radical.

Particular preference is given to disazo dyes of the formulae Ia, Ib (including in particular those where X¹ =OH and X² =NH₂), If, Ih, Ij, Ik, Im and In.

Of particular importance are mixtures of dyes of the formula Ic where X¹ is hydroxyl and X² is amino and Id where Y is carbonyl. Of these, particularly suitable mixtures are those where R⁶ and R⁸ are each hydrogen and R⁷ is a radical of the formula SO₂ --N(Ar)Alk where Ar and Alk are each as defined above.

Particular preference is further given to mixtures of dyes Ic and Id where the dyes of the formulae Ic and Id are present in a weight ratio of from 30:70 to 70:30.

In addition, preference is given to disazo dyes of the formula I in which the substituents are selected from a combination of the above-recited preferred substituents.

The novel disazo dyes of the formula I are obtainable in a conventional manner.

For example, they can be obtained by diazotizing an aniline of the formula VI ##STR15## where R¹, R², R³, R⁴ and R⁵ are each as defined above, in a conventional manner and coupling the resulting diazonium salt with a naphthalene of the formula VII ##STR16## where X¹ and X² are each as defined above.

The resulting monoazo dye of the formula VIII ##STR17## where R¹, R², R³, R⁴, R⁵, X¹ and X² are each as defined above, can then be coupled with a diazonium salt derived from an aniline of the formula IX ##STR18## where R⁶, R⁷ and R⁸ are each as defined above.

It will be appreciated that the dyes can also be obtained by the reverse sequence, by diazotizing D² --NH₂ and coupling with the naphthalene of the formula VII and then diazotizing D¹ --NH₂ and coupling with the resulting dye.

The dyes of the formula I according to the invention are advantageously useful for dyeing natural or synthetic substrates, in particular wool, leather or polyamide.

The dyeings obtained have black and blue to navy shades and good lightfastness and also good wetfastness properties.

The novel dyes can be applied alone and mixed with one another or else mixed with other dyes.

The present invention further encompasses a process for dyeing wool at a pH of from 3 to 7 by using disazo dyes containing an SO₂ --C₂ H₄ --Q¹ radical. The prior art azo class reactive dyes require special dyeing processes for wool. It has now been found that the novel reactive dyes, especially those of the formula III where R¹⁰ is a radical of the formula SO₂ --C₂ H₄ --Q¹, lead to excellent dyeing results by conventional wool-dyeing methods under acidic conditions.

The present invention further provides sulfonamides of the formula X ##STR19## where the ring A may be benzo-fused,

Alk is C₁ -C₈ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl,

U¹ is hydrogen, C₁ -C₄ -alkyl which may be substituted by C₁ -C₄ -alkoxy or phenyl, or is halogen, and

U² is a radical of the formula SO₂ --CH═CH₂ or SO₂ --C₂ H₄ --Q, where Q is hydroxyl or an alkali-detachable group

and the sulfonamide is in the 3- or 4-position.

The present invention further provides sulfonamides of the formula XI ##STR20## where n is 1 or 2,

Alk is C₁ -C₈ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C₅ -C8-cycloalkyl

and the sulfonamide is in the 3- or 4-position.

As regards exemplification of the substituents Alk, U¹ and U², the observations made above refer.

The novel sulfonamides of the formula X are obtainable in a conventional manner.

For example, they can be obtained by reacting an anilinesulfonic acid of the formula XII ##STR21## where the ring A, Alk and U¹ are each as defined above, with 4-acetylaminobenzenesulfonyl chloride and converting the resulting sulfonamide, for example with thionyl chloride or chlorosulfonic acid, into the corresponding sulfonyl chloride of the formula XIII ##STR22## where the ring A, Alk and U¹ are each as defined above. Reducing the sulfonyl chloride group gives the sulfinic acid, which, for example by reaction with ethylene oxide, can be made to yield the compound of the formula XIV ##STR23## where the ring A, Alk and U¹ are each as defined above.

The sulfonamides of the formula X are obtained by customary deacetylation and/or esterification reactions.

The novel sulfonamides of the formula XI are likewise obtainable in a conventional manner.

For example, they can be obtained by reacting a naphthalenesulfonic acid of the formula XV ##STR24## where n and Alk are each as defined above, with 4-acetylaminobenzenesulfonyl chloride and deacetylating the resulting sulfonamide in a conventional manner.

The sulfonamides of the formulae X and XI are useful intermediates for dye synthesis, especially for synthesizing the disazo dyes of the formula I.

The Examples which follow illustrate the invention.

EXAMPLE 1

46.8 g of the red dye of the formula ##STR25## were dissolved in 200 ml of water at pH 7 (sodium hydroxide solution) and at room temperature. To the solution was added, simultaneously with sodium bicarbonate, the suspension of a diazonium salt prepared as follows:

35.8 g of the diazo component of the formula ##STR26## were dissolved in 200 ml of water at pH 11 and then admixed with 31 ml of 23% strength by weight aqueous sodium nitrite solution. The solution was then stirred out onto 100 ml of 18.5% strength by weight hydrochloric acid cooled with ice to 0° C. The mixture was subsequently stirred at from 0 to 5° C. for 1 h, and excess nitrous acid was then destroyed.

The reaction mixture was subsequently stirred at pH 6.5-7 for 2 h. Thereafter the mixture was spray-dried.

This gave 89.5 g of the dye of the formula ##STR27##

The black powder still comprised about 35 g of sodium chloride and 4 g of water. The dye forms a blue solution in water and dyes wool in a navy shade having excellent lightfastness.

The absorption spectrum in water has a maximum at 600 nm (pH about 4).

EXAMPLE 2

a) 24 g of 2-aminodiphenyl sulfone were stirred overnight with 110 ml of 30% strength by weight hydrochloric acid and 0.1 g of an acidic wetting agent. A little ice was then added to cool down to 0° C., and 31.5 ml of 23% strength by weight aqueous sodium nitrite solution were added dropwise. The diazotization was complete after a further two hours of stirring. Excess nitrous acid was destroyed with sulfamic acid.

The resulting diazonium salt solution was admixed over 90 min of very thorough stirring with 31.9 g of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid dissolved in 200 ml of water at pH 5.8. This gave a suspension of the red dye of the formula ##STR28## b) 33 g of the diazo component of the formula ##STR29## were dissolved in 450 ml of water and 1 g of an alkaline wetting agent at 50° C. and at pH 11 (sodium hydroxide solution). To the solution were added 35 ml of 23% strength by weight aqueous sodium nitrite solution, and the mixture was then poured onto a mixture of 300 ml of water and 40 ml of concentrated hydrochloric acid. The mixture was subsequently stirred at from 40 to 45° C. for 4 h. Excess nitrous acid was then destroyed.

c) The reaction mixtures described in a) and b) were then combined and the pH of the mixture was adjusted to 6-7.5 with dilute sodium hydroxide solution. The mixture was subsequently stirred for 1 h, adjusted to pH 9 and stirred overnight. The resulting blue suspension was heated to 70° C. and the dye of the formula ##STR30## was precipitated with concentrated hydrochloric acid and filtered off with suction. Drying left 88 g of a black powder which dyes wool and polycaprolactam fabric in a navy to black shade (λ_(max) in water: 582 nm; shoulder at 626 nm).

EXAMPLE 3

a) 38.0 g of the diazo component of the formula ##STR31## were added to 100 ml of 18.5% strength by weight hydrochloric acid a little at a time and stirred in overnight at room temperature. The mixture was then cooled down to 0° C. with ice and admixed with 31.5 ml of 23% by weight aqueous sodium nitrite solution. Excess nitrous acid was destroyed after stirring for one hour.

b) 31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid were dissolved in 600 ml of water at pH 6 (sodium hydroxide solution). This solution was added with very thorough stirring to the diazonium salt suspension described under a), which had been diluted with 600 ml of water beforehand. The coupling mixture was stirred overnight at from 20 to 25° C. The pH of the mixture was then adjusted to 4 with sodium acetate.

c) 24.5 g of the diazo component of the formula ##STR32## were stirred for 1 h at from 30 to 60° C. with 30.5 g of concentrated hydrochloric acid and 300 ml of water. The mixture was then admixed with 0.7 g of an acidic wetting agent and thereafter 35 ml of 23% strength by weight aqueous sodium nitrite solution were added dropwise over 10 min, and subsequently stirred at 30° C. for 2 h. Excess nitrous acid was then destroyed and the diazonium salt solution was poured into the coupling mixture described under b). The pH of the 2nd coupling reaction was raised to 6-6.5 with sodium bicarbonate and the coupling was completed by stirring overnight.

The dye of the formula ##STR33## was precipitated with hydrochloric acid. Filtering off with suction and drying left 104.5 g of a black powder which gives a blue solution in water (λ_(max) : 577 nm) and dyes polycaprolactam and wool in a navy shade having good fastness properties.

EXAMPLE 4

33 g of the diazo component of the formula ##STR34## were dissolved in 450 ml of water at 80° C. and pH 11 (sodium hydroxide solution). The solution was admixed with 0.5 g of an acidic wetting agent and 35 ml of 23% strength by weight sodium nitrite solution. The suspension obtained was stirred out onto a mixture of 300 ml of water and 40 ml of concentrated hydrochloric acid. The mixture was subsequently stirred at from 35 to 40° C. for 4 h. Excess nitrous acid was then destroyed and the pH of the suspension was raised to 1.6 with sodium bicarbonate. Thereafter 31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, dissolved in 150 ml of water at pH 5.8 - 6, were added dropwise over 1.5 h. The temperature was 30-35° C. The reaction mixture was stirred overnight at pH 2 and was then mixed with a diazonium salt solution prepared as follows:

24.5 g of the diazo component of the formula ##STR35## were diazotized similarly to Example 3.

The coupling with the above-described red intermediate of the formula ##STR36## was carried out by gradually raising the pH of the mixture to 7.5 with dilute sodium hydroxide solution, subsequently stirring it at pH 7.5 for 30 min and then adjusting it with sodium hydroxide solution to pH 9.

The dye of the formula ##STR37## was precipitated by acidifying the reaction mixture to pH 0.5 and additionally adding sodium chloride. Filtering off with suction drying left 144 g of a black powder still comprising about 50 g of salt.

The dye dissolved in water at about pH 4 has a UV-VIS maximum at 575 nm. It dyes wool, polyamide and leather in a fast blue to navy shade.

EXAMPLE 5

61.1 g of the red dye of the formula ##STR38## were dissolved at room temperature in 500 ml water at pH 6-7 (sodium bicarbonate). 22.2 g of 4-aminophthalic N-(3-hydroxypropyl)imide were then diazotized by dissolving in 33 ml of concentrated hydrochloric acid and water, cooling with ice to -3° C. and adding 31 ml of 23% strength by weight aqueous sodium nitrite solution. After subsequent stirring at 0-5° C. for 20 min excess nitrous acid was destroyed with sulfamic acid. The resulting diazonium salt solution was added over 30 min to the above-prepared solution in such a way that the pH of the reaction mixture could be held continuously within the range from 6 to 7.8 with sodium bicarbonate. The resulting blue dye solution was spray-dried at pH 6.5. This gave a black powder of the dye of the formula ##STR39##

It gives a blue solution in water and dyes wool and polyamide in a bright blue to bluish black shade having excellent wetfastness properties.

The absorption maximum in water at about pH 4 is 590 nm.

EXAMPLE 6

37.5 g of the diazo component of the formula ##STR40## were dissolved in 250 ml of water at pH 10 (sodium hydroxide solution) and thereafter admixed with 31.5 ml of 23% strength by weight aqueous sodium nitrite solution. The mixture was stirred out onto 100 ml of the 18.5% strength by weight hydrochloric acid which had been cooled down to -2° C. with ice in such a way that the temperature was ≦5° C. Initially this produced a solution, from which the diazonium salt separated as a precipitate. After 60 min of stirring at 0-5° C. excess nitrous acid was destroyed. A freshly prepared aqueous solution of 38.5 g of 83.2% by weight 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid was then added dropwise over 1.5 h and the temperature of the reaction mixture was raised to 22° C. Stirring overnight gave a thick suspension of the dye of the formula ##STR41## (This dye dissolves on high dilution in water with a red color, the solution having an absorption maximum at 517 nm at pH 3-4 and an absorption maximum at 549 nm at pH 10.)

The mixture was then neutralized with sodium hydroxide solution and admixed with the diazonium salt of 1-aminoanthraquinone, which had been diazotized in a conventional manner in sulfuric acid with nitrosylsulfuric acid and had been isolated in crystalline form following precipitation with ice. At pH 5-8 the diazonium salt was coupled to form the blue dye of the formula ##STR42##

Titrating the reaction mixture, precipitating the dye with potassium chloride, filtering off with suction, washing with aqueous potassium chloride solution and drying left 165 g of a black powder having a dye content of about 61% as potassium salt.

The dye gives a blue solution in water (λ_(max) : 604 nm and 400 nm at pH ˜4) and dyes wool in a strong dark blue shade having excellent fastness properties.

EXAMPLE 7

43.5 g of the diazo component of the formula ##STR43## were dissolved in 400 ml of water under weakly acidic conditions (sodium bicarbonate). The mixture was then cooled down to 0° C., and 27 ml of 30% strength by weight hydrochloric acid were added, followed by 31.5 ml of 23% strength of aqueous sodium nitrite solution. The mixture was subsequently stirred at 5° C. for 2 h. Excess nitrous acid was then destroyed and the mixture was stirred out onto a freshly prepared precipitation of 38.5 g of 83.2% strength by weight 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid of pH<1. The reaction mixture was stirred overnight at room temperature. This gave the red dye of the formula ##STR44##

The absorption maximum of an aqueous solution (pH 3-4) has a maximum at 518 nm, and the maximum at pH 7.9 is at 546 nm.

A mixture of 10.3 g of 3-aminophthalic N-(₂ -hydroxyethyl)imide and 10.3 g of 4-aminophthalic N-(2-hydroxyethyl)imide dissolved in 35 ml of concentrated hydrochloric acid and 75 ml of water at 0-5° C. was then diazotized in a conventional manner with sodium nitrite. Following the destruction of excess nitrous acid the diazonium salt solution was added to the above-described red coupling mixture. The mixture was then neutralized by stirring with sodium bicarbonate.

The result obtained was a deep blue solution of the dyes of the formulae ##STR45##

The dye mixture dyes wool in a navy shade having good light- and wetfastness properties.

The dyes listed in the tables below are obtained in a similar manner.

                  TABLE 1                                                          ______________________________________                                           #STR46##                                                                       Ex.                               Hue on                                       No. Q wool                                                                   ______________________________________                                            -                                                                             8                                                                                                              blue 7##                                        - 9                                                                                                           blue 8##                                        - 10                                                                                                          blue 9##                                        - 11                                                                                                          blue 0##                                        - 12                                                                                                          blue 1##                                        - 13                                                                                                          blue 2##                                        - 14                                                                                                          blue 3##                                        - 15                                                                                                          blue 4##                                        - 16                                                                                                          blue 5##                                        - 17                                                                                                          blue 6##                                        - 18                                                                                                          blue 7##                                        - 19                                                                                                          blue58##                                     ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________       #STR59##                                                                        -                                                                           Ex.                                                                              No. Q E.sup.1 E.sup.2 Hue on wool                                            __________________________________________________________________________       20                                                                                                                   H H  bluish black                         - 21                                                                                                                H H  bluish black                         - 22                                                                                                                H H  bluish black                         - 23                                                                                                                H H  bluish black                         - 24                                                                                                                H H  bluish black                         - 25                                                                                                                H H  bluish black                         - 26                                                                                                                H H  bluish black                         - 27                                                                                                                NHCOCH.sub.3 H  bluish black                                                   - 28                                                                           H H  bluish black                         - 29                                                                                                                H H  bluish black                         - 30                                                                                                                CH.sub.3 H  bluish black                  - 31                                                                                                                CH.sub.3 CH.sub.3  bluish              __________________________________________________________________________                                           black                               

                                      TABLE 3                                      __________________________________________________________________________       #STR72##                                                                        -                                                                           Ex.                                                                              No. Q E Hue on wool                                                          __________________________________________________________________________       32                                                                                                              H navy #                                       - 33                                                                                                           H navy #                                       - 34                                                                                                           H navy #                                       - 35                                                                                                           H navy #                                       - 36                                                                                                           H navy #                                       - 37                                                                                                           H navy #                                       - 38                                                                                                           H navy #                                       - 39                                                                                                           H navy #                                       - 40                                                                                                           H navy #                                       - 41                                                                                                           H navy #                                       - 42                                                                                                           H navy #                                       - 43                                                                                                           H navy #                                       - 44                                                                                                           H navy #                                       - 45                                                                                                           H navy #                                       - 46                                                                                                           H navy #                                       - 47                                                                                                           H navy #                                       - 48                                                                                                           CH.sub.3 navy                                  - 49                                                                                                           CH.sub.3 navy                                  - 50                                                                                                           CH.sub.3 navy                               __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________       #STR92##                                                                        -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 Q Hue on wool                                    __________________________________________________________________________       51 H CH.sub.3 CH.sub.3                                                                                                   bluish black                          - 52 H H H                                                                                                              bluish black                          - 53 H CH.sub.3 CH.sub.3                                                                                                bluish black                          - 54 H H CH.sub.3                                                                                                       bluish black                          - 55 CH.sub.3 CH.sub.3 H                                                                                                bluish black                          - 56 H H H                                                                                                              bluish black                          - 57 H H H                                                                                                              bluish black                          - 58 H H H                                                                                                              bluish black                          - 59 H H H                                                                                                              bluish black                          - 60 H H H                                                                                                              bluish black                          - 61 NHCOCH.sub.3 H OCH.sub.3                                                                                           bluish black                          - 62 NHCOCH.sub.3 H OCH.sub.3                                                                                           bluish black                          - 63 H H H                                                                                                              bluish black                          - 64 H H H                                                                                                              bluish black                          - 65 H H CH.sub.3                                                                                                       bluish black                          - 66 H H CH.sub.3                                                                                                       bluish black                          - 67 H H CH.sub.3                                                                                                       bluish black                          - 68 H H H                                                                                                              bluish black                          - 69 H H CH.sub.3                                                                                                       bluish black                          - 70 CH.sub.3 H CH.sub.3                                                                                                bluish black                          - 71 CO.sub.2 H H H                                                                                                     bluish black                          - 72 H CH.sub.3 H                                                                                                       bluish black                          - 73 H CH.sub.3 H                                                                                                       bluish black                          - 74 H H H                                                                                                              bluish black                       __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________       #STR117##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 Hue on wool                                      __________________________________________________________________________       75 H                                                                                                           H reddish blue                                  - 76 Cl                                                                                                       H reddish blue                                  - 77 CN                                                                                                       H dark blue                                     - 78 CO.sub.2 CH.sub.3 SO.sub.3 H H reddish blue                              79 CO.sub.2 C.sub.2 H.sub.5 SO.sub.3 H H reddish blue                          80 CN SO.sub.3 H H reddish blue                                                 - 81 Br                                                                                                       H reddish blue                                  - 82 H SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 SO.sub.3 H reddish blue                                        83 H SO.sub.2 CH.sub.2 CH.sub.2 OH                                            SO.sub.3 H reddish blue                          84 H SO.sub.2 CH.sub.2 CH.sub.2 OCHO SO.sub.3 H reddish blue                   85 H SO.sub.2 CH═CH.sub.2 SO.sub.3 H reddish blue                          86 H SO.sub.2 CH.sub.2 CH.sub.2 Cl SO.sub.3 H reddish blue                     87 H SO.sub.2 CH.sub.2 CH═CH.sub.2 SO.sub.3 H reddish blue                 88 H SO.sub.2 C.sub.2 H.sub.5 SO.sub.3 H reddish blue                          89 H SO.sub.2 C.sub.6 H.sub.5 SO.sub.3 H reddish blue                          90 SO.sub.3 H SO.sub.2 C.sub.6 H.sub.5 H reddish blue                          91 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H reddish blue                  - 92 SO.sub.3 H                                                                                               H reddish blue                                  - 93 COC.sub.6 H.sub.5 Cl SO.sub.3 H reddish blue                           __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________       #STR123##                                                                       -                                                                           Ex.                        Hue on                                                No. E.sup.1 E.sup.2 E.sup.3 wool                                             __________________________________________________________________________      94                                                                               SO.sub.3 H                                                                         CH.sub.2 CH.sub.2 OH                                                                            H  blue                                                   95 SO.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.3 H blue                               96 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H blue                      97 SO.sub.3 H CH.sub.3 H blue                                                  98 SO.sub.3 H C.sub.2 H.sub.5 H blue                                           -  99 H                                                                                                  H blue ##                                            - 100 H                                                                                                  H blue ##                                            - 101 SO.sub.3 H C.sub.4 H.sub.8 OH(n) H blue                                 102 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                  H blue                                                 - 103 H                                                                                                  H blue ##                                            - 104 H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH H blue                        105 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H blue                                    106 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                     CH.sub.2 OCOCH.sub.3 H blue                           107 SO.sub.3 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                 H blue                                                108 SO.sub.3 H C.sub.2 H.sub.5 Cl blue                                         109 SO.sub.3 H C.sub.2 H.sub.4 OH Cl blue                                      110 H CH.sub.2 CO.sub.2 H H blue                                                - 111 H                                                                                                  H blue7##                                         __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________       #STR128##                                                                       -                                                                           Ex.                                      Hue on                                  No. E.sup.3 Y E.sup.1 E.sup.2 wool                                           __________________________________________________________________________       112 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                                      ,1 reddish ,1 blue                    - 113 SO.sub.3 H CO CH.sub.2 CH.sub.2 OCH.sub.3                                                                         ,1 reddish ,1 blue                    - 114 H CO                                                                                                             #STR131##                                                                       ,1 reddish ,1 blue                    - 115 H CO                                                                                                             #STR133##                                                                       ,1 reddish ,1 blue                    - 116 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                          ,1 reddish ,1 blue                    - 117 SO.sub.3 H CH.sub.2 C.sub.2 H.sub.5                                                                               ,1 dark ,1 blue                       - 118 SO.sub.3 H CO CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                              ,1 reddish ,1 blue                    - 119 SO.sub.3 H CO CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                   ,1 dark ,1 blue                       - 120 SO.sub.3 H CO CH.sub.2 C.sub.6 H.sub.5                                                                            ,1 reddish ,1 blue                    - 121 SO.sub.3 H CO CH.sub.2 C.sub.6 H.sub.5                                                                            ,1 dark ,1 blue                       - 122 SO.sub.3 H CH.sub.2 C.sub.4 H.sub.9                                                                               ,1 dark ,1 blue                       - 123 CH.sub.3 CO                                                                                                      #STR142##                                                                       ,1 dark ,1 blue                       - 124 CH.sub.3 CO                                                                                                      #STR144##                                                                       ,1 dark ,1 blue                       - 125 H CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                                   ,1 dark ,1 blue                       - 126 H CO CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                                      ,1 dark ,1 blue                       - 127 H CH.sub.2                                                                                                       #STR148##                                                                      blue149##                           __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________       #STR150##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool                              __________________________________________________________________________     128 NO.sub.2  H   CH.sub.3                                                                              H      grayish blue                                     129 NO.sub.2 H CH.sub.3 CH.sub.3 grayish blue                                  130 NO.sub.2 CH.sub.3 CH.sub.3 H grayish blue                                  131 NO.sub.2 CH.sub.3 OCH.sub.3 H grayish blue                                 132 NO.sub.2 H OCH.sub.3 H grayish blue                                        133 NO.sub.2 H OC.sub.2 H.sub.5 H grayish blue                                 134 NO.sub.2 H OC.sub.4 H.sub.9 H grayish blue                                 135 NO.sub.2 CH.sub.3 H CH.sub.3 grayish blue                                  136 NO.sub.2 H C.sub.2 H.sub.5 H grayish blue                                  137 NO.sub.2 H OCH.sub.3 NHCOCH.sub.3 grayish blue                             138 SO.sub.2 O--C.sub.6 H.sub.5 H OCH.sub.3 H grayish blue                     139 SO.sub.2 C.sub.2 H.sub.4 OH H CH.sub.3 CH.sub.3 grayish blue                                              140 SO.sub.2 CH.sub.2 CH═CH.sub.2 H                                       OCH.sub.3 H grayish blue                         141 SO.sub.2 CH═CH.sub.2 H CH.sub.3 CH.sub.3 grayish blue                  142 SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 H CH.sub.3 CH.sub.3 grayish                                       blue                                             143 SO.sub.2 N(CH.sub.3).sub.2 H OCH.sub.3 H grayish blue                      144 SO.sub.2 CH═CH.sub.2 H NHCOCH.sub.3 H grayish blue                     145 SO.sub.2 CH.sub.2 CH.sub.2 OH H NHCOCH.sub.3 H grayish blue              __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________       #STR151##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 Q Hue on wool                                            __________________________________________________________________________       146 CH.sub.2 CH.sub.2 OSO.sub.3 H H                                                                                                   reddish blue                                                                   - 147 CH.sub.2                                                               CH.sub.2 OCOCH.sub.                                                            3 H                                                                              reddish blue                                                                   - 148 C.sub.2                                                                H.sub.5 H                                                                        reddish blue                                                                   - 149 CH.sub.2                                                               CH.sub.2 OCHO                                                                  SO.sub.2 N(CH.sub.3                                                            ).sub.2                                                                          reddish blue                                                                   - 150 CH.sub.2                                                               CH.sub.2 OCOCH.sub.                                                            3 SO.sub.2                                                                     N(CH.sub.3).sub.2                                                                reddish blue                                                                   - 151 CH.sub.3                                                               SO.sub.2 NHCH.sub.2                                                             CH.sub.2 OH                                                                     reddish blue                                                                   - 152 CH.sub.2                                                               CH.sub.2 OH H                                                                    reddish blue                                                                   - 153 CH.sub.2                                                               CH.sub.2 OH H                                                                    reddish blue                                                                   - 154 CH.sub.2                                                               CH.sub.2 OH H                                                                    reddish blue                                                                   - 155 CH.sub.2                                                               CH.sub.2 OH                                                                    SO.sub.2 N(CH.sub.3                                                            ).sub.2                                                                          reddish blue                                                                   - 156 CH.sub.2                                                               CH.sub.2 OH                                                                    SO.sub.2 N(CH.sub.3                                                            ).sub.2                                                                          reddish blue                                                                   - 157 CH.sub.3                                                               SO.sub.2 N(C.sub.2                                                             H.sub.5).sub.2                                                                   reddish blue                                                                   - 158 C.sub.2                                                                H.sub.5 H                                                                        reddish blue                                                                   - 159 C.sub.2                                                                H.sub.5 SO.sub.2                                                               N(CH.sub.3).sub.2                                                                reddish blue                                                                   - 160 CH.sub.2                                                               CH.sub.2 OSO.sub.3                                                             H H                                                                              reddish blue                                                                   - 161 CH.sub.3                                                               SO.sub.3 H                                                                       reddish blue                                                                   - 162 C.sub.2                                                                H.sub.5 SO.sub.3 H                                                               reddish blue                                                                   - 163 C.sub.2                                                                H.sub.5 SO.sub.3 H                                                               reddish blue                                                                   - 164 OH                                                                       #STR170##                                                                      reddish blue          __________________________________________________________________________

                                      TABLE 10                                     __________________________________________________________________________       #STR172##                                                                       -                                                                                                                                       Hue                  Ex.      on                                                                    No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 wool                             __________________________________________________________________________       165 CO.sub.2 CH.sub.3 SO.sub.2 OC.sub.6 H.sub.5 H                                                                                          SO.sub.3 H                                                                   ,1 blu- ,1                                                                     ish ,1 black                                                                     - 166                                                                        CO.sub.2                                                                       CH.sub.3                                                                       SO.sub.3 H H                                                                     H  ,1 blu-                                                                   ,1 ish ,1                                                                      black                                                                            - 167                                                                        CO.sub.2                                                                       CH.sub.3                                                                       SO.sub.3 H H                                                                     H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 168 CO.sub.2 CH.sub.3 SO.sub.3 H H                                                                                                      H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 169 CO.sub.2 CH.sub.3                                                                                                                   SO.sub.3 H                                                                     H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 170 CO.sub.2 CH.sub.3 SO.sub.2 N(CH.sub.3).sub.2 SO.sub.3 H                                                                             H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 171 CO.sub.2 CH.sub.3 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H                                                                               SO.sub.3 H                                                                   ,1 blu- ,1                                                                     ish ,1 black                                                                     - 172 CN                                                                     SO.sub.2                                                                       N(CH.sub.3).su                                                                 b.2 SO.sub.3                                                                   H                                                                                H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 173 Br SO.sub.2 N(CH.sub.3).sub.2 SO.sub.3 H                                                                                            H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 174                                                                                                                                     SO.sub.2                                                                     N(C.sub.2                                                                      H.sub.4                                                                        OH).sub.2                                                                      SO.sub.3 H                                                                       H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 175                                                                                                                                     #STR185##                                                                      SO.sub.3 H                                                                     H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 176                                                                                                                                     #STR188##                                                                      SO.sub.3 H                                                                     H  ,1 redd-                                                                  ,1 ish ,1                                                                      blue                  - 177 CO.sub.2 CH.sub.3 SO.sub.3 H CH.sub.3                                                                                               H  ,1 blu-                                                                   ,1 ish ,1                                                                      black                                                                            - 178                                                                        CO.sub.2                                                                       CH.sub.3                                                                       SO.sub.3 H H                                                                     CH.sub.3                                                                     ,1 blu- ,1                                                                     ish ,1 black                                                                     - 179 H                                                                        H TR193##                                                                      SO.sub.3 H                                                                   ,1 dark ,1                                                                     blue               __________________________________________________________________________

                                      TABLE 11                                     __________________________________________________________________________       #STR195##                                                                       -                                                                           Ex. No.                                                                            E.sup.1      E.sup.2         E.sup.3   E.sup.4                             __________________________________________________________________________                                                             Hue on wool                                                                     180 H NO.sub.2 H                                                              CH.sub.2 CH.sub.2                                                              OH reddish blue                                                                 181 H NO.sub.2 H                                                              CH.sub.2 CH.sub.2                                                              CH.sub.2 OH                                                                    reddish blue                                                                    182 H NO.sub.2 H                                                              CH.sub.2 C.sub.6                                                               H.sub.5 reddish                                                                blue                     183 H NO.sub.2 H (CH.sub.2).sub.2 OCH.sub.3 reddish blue                       184 H NO.sub.2 H (CH.sub.2).sub.3 OCH.sub.3 reddish blue                       185 H NO.sub.2 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 reddish                                                                blue                      - 186 H NO.sub.2 H                                                                                                                     reddish blue                                                                  - 187 H                                                                      NO.sub.2 H                                                                        reddish blue                                                                  - 188 H                                                                      NO.sub.2 H                                                                        reddish blue                                                                  - 189 SO.sub.2                                                               C.sub.6 H.sub.5 H                                                              H                                                                                 reddish blue                                                                  - 190                                                                          H H 200##                                                                       reddish blue                                                                  - 191 SO.sub.2                                                               C.sub.6 H.sub.5                                                                CH.sub.3 H                                                                        reddish blue                                                                  - 192                                                                          SO.sub.3 H H                                                                 C.sub.4 H.sub.9                                                                reddish blue                                                                     - 193 SO.sub.2                                                               C.sub.6 H.sub.5 H                                                              SO.sub.3 H                                                                     C.sub.4 H.sub.9                                                                reddish blue                                                                     - 194                                                                          H SO.sub.3 H                                                                 C.sub.4 H.sub.9                                                                reddish blue                                                                     - 195 SO.sub.2                                                               C.sub.6 H.sub.5 H                                                              SO.sub.2 CH.sub.2                                                              CO.sub.2 H                                                                     C.sub.2 H.sub.4                                                                OH  reddish blue                                                                196 SO.sub.2                                                                  C.sub.6 H.sub.5 H                                                              SO.sub.2 CH.sub.2                                                              CO.sub.2 H                                                                     CH.sub.2 C.sub.6                                                               H.sub.5  reddish                                                               blue                     197 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.2 CH.sub.3 CH.sub.2 C.sub.6                                                                    H.sub.5  reddish                                                               blue                      - 198                                                                                                                                 H SO.sub.2                                                                   CH.sub.2 CO.sub.2                                                              H CH.sub.2                                                                     C.sub.6 H.sub.5                                                                reddish blue                                                                     - 199 H                                                                      SO.sub.2 --O--C.su                                                             b.6 H.sub.5 H                                                                     reddish blue                                                                  - 200 H                                                                      SO.sub.2 --O--C.su                                                             b.6 H.sub.5 H                                                                     reddish blue                                                                  - 201 H                                                                        H C.sub.2                                                                    H.sub.4 OH                                                                     reddish blue                                                                     - 202 H                                                                        H C.sub.4                                                                    H.sub.9  reddish                                                               blue                      - 203 H                                                                                                                               H CH.sub.2                                                                   CH.sub.2 C.sub.6                                                               H.sub.5  reddish                                                               blue                      - 204 H                                                                                                                               H C.sub.4                                                                    H.sub.9  reddish                                                               blue                      - 205 H SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2 H CH.sub.2 C.sub.6                                                                     H.sub.5  reddish                                                               blue                     206 H SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H CH.sub.2 C.sub.6                                                                 H.sub.5  reddish                                                               blue                     207 H SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H CH.sub.2 C.sub.6                                                                 H.sub.5  reddish                                                               blue                     208 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H CH.sub.2 CH.sub.2                                                                 C.sub.6 H.sub.5                                                                reddish blue                                                                    209 SO.sub.3 H                                                                SO.sub.2 N(C.sub.2                                                              H.sub.5) 2 H                                                                  CH.sub.2 C.sub.6                                                               H.sub.5  reddish                                                               blue                      - 210 SO.sub.3 H                                                                                                                      H CH.sub.2                                                                   C.sub.6 H.sub.5                                                                reddish blue                                                                     - 211 SO.sub.3                                                               H                                                                                H CH.sub.2                                                                   CH.sub.2 C.sub.6                                                               H.sub.5  reddish                                                               blue                      - 212 H                                                                                                                               H C.sub.2                                                                    H.sub.5  reddish                                                               blue                      - 213 H                                                                                                                               H CH.sub.2                                                                   CH.sub.2 C.sub.6                                                               H.sub.5  reddish                                                               blue                      - 214 H                                                                                                                               H CH.sub.2                                                                   C.sub.6 H.sub.5                                                                reddish blue                                                                     - 215 H                                                                        H C.sub.4                                                                    H.sub.9  reddish                                                               blue                      -      Hue on wool/                                                                .sub.max [nm]                                                                  at pH 4                                                                   216 SO.sub.2 OC.sub.6 H.sub.5 H H CH.sub.2 C.sub.6 H.sub.5  reddish                                                                  blue                      - 217 SO.sub.2 OC.sub.6 H.sub.5 H H                                                                                                    reddish blue                                                                  - 218 CH.sub.3                                                               H                                                                                #STR219##                                                                       reddish blue                                                                  - 219 H                                                                      SO.sub.2 CH.sub.2                                                              CH.sub.2 OSO.sub.3                                                              H H CH.sub.2                                                                  CH.sub.2 C.sub.6                                                               H.sub.5 392 and                                                                593                      220 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 CH.sub.2                                                                     CH.sub.2 OC.sub.2                                                              H.sub.5 392 and                                                                594                      221 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 C.sub.6 H.sub.5                                                              392 and 593                                                                     222 H SO.sub.2                                                                CH.sub.2 CH.sub.2                                                              OSO.sub.3 H H                                                                  CH.sub.2 CH.sub.2                                                              CH.sub.2 OCH.sub.3                                                              392 and 594                                                                    223 H SO.sub.2                                                                CH.sub.2 CH.sub.2                                                              Cl H CH.sub.2                                                                  CH.sub.2 OC.sub.4                                                              H.sub.9 392 and                                                                594                      224 H SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 H CH.sub.2 CH.sub.2                                                                     OCH.sub.2 C.sub.6                                                              H.sub.5 392 and                                                                593                       - 225 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H                                                                                      393 and 591                                                                    - 226 H                                                                      SO.sub.2 CH.sub.2                                                              CH.sub.2 OSO.sub.3                                                              H H                                                                             393 and 591                                                                    - 227 H                                                                      SO.sub.2 CH═CH                                                             .sub.2 H                                                                         394 and 595                                                                    - 228 H                                                                      SO.sub.2 CH.sub.2                                                              CH.sub.2 OCOCH.sub                                                             .3 H                                                                              reddish blue                                                                  - 229 H                                                                      SO.sub.2 CH.sub.2                                                              CH.sub.2 Cl H                                                                     reddish blue                                                                  - 230 SO.sub.3                                                               H SO.sub.2                                                                     CH.sub.2 CH.sub.2                                                              OSO.sub.3 H H                                                                  C.sub.4 H.sub.9                                                                reddish blue                                                                     - 231 SO.sub.3                                                               H SO.sub.2                                                                     CH.sub.2 CH.sub.2                                                              OSO.sub.3 H H                                                                     reddish blue                                                                  - 232 SO.sub.2                                                               CH.sub.2 CH.sub.2                                                              OSO.sub.3 H H H                                                                CH.sub.2 CH.sub.2                                                              OH  reddish blue                                                                233 H H SO.sub.2                                                              CH.sub.2 CH.sub.2                                                              OSO.sub.3 H                                                                    CH.sub.2 C.sub.6                                                               H.sub.5 reddish                                                                blue                     234 H NO.sub.2 H (CH.sub.2).sub.5 CO.sub.2 H reddish blue                       - 235 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H                                                                                       reddish             __________________________________________________________________________                                                             blue              

                                      TABLE 12                                     __________________________________________________________________________       #STR228##                                                                       -                                                                           Ex. No.                                                                            E.sup.1       E.sup.2       Hue on wool                                    __________________________________________________________________________     236 CH.sub.2 CH=CH.sub.2                                                                         CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9                                                           reddish blue                                      - 237                                                                                                         CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                            reddish blue                                      - 238                                                                                                         CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                            reddish blue                                      - 239                                                                                                         CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                            reddish blue                                      - 240                                                                                                         CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                            reddish blue                                      - 241                                                                                                         CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                            reddish blue                                      - 242                                                                                                         CH.sub.2 C.sub.6 H.sub.5 reddish blue                                          - 243 C.sub.2 H.sub.4 OH                                                       reddish blue                                    - 244 C.sub.3 H.sub.6 OH                                                                                      reddish blue                                    - 245 C.sub.4 H.sub.8 OH                                                                                      reddish blue                                    - 246 CH.sub.2 C.sub.6 H.sub.5                                                                                reddish blue                                    - 247 C.sub.2 H.sub.4 OH                                                                                      reddish blue                                    - 248                                                                                                         C.sub.4 H.sub.9 reddish blue                 __________________________________________________________________________

                                      TABLE 13                                     __________________________________________________________________________       #STR241##                                                                       -                                                                           Ex. No.                                                                            E.sup.1       E.sup.2    E.sup.3    Hue on wool                            __________________________________________________________________________       249                                                                                                                    H H reddish blue                        - 250                                                                                                                 H H reddish blue                        - 251                                                                                                                 H SO.sub.2 CH.sub.3 blue                                                       - 252                                                                          H SO.sub.2 CH.sub.2 CO.sub.2 H                                               blue                                      - 253 SO.sub.2 OC.sub.6 H.sub.5 H H reddish blue                              254 SO.sub.2 OC.sub.6 H.sub.5 CH.sub.3 H reddish blue                          255 SO.sub.2 OC.sub.6 H.sub.5 H H reddish blue                                  - 256 H                                                                                                               H blue ##                               - 257 H                                                                                                               H blue ##                               - 258 H H                                                                                                             blue 48##                               - 259 H H SO.sub.2 OC.sub.6 H.sub.5 blue                                      260 Cl H SO.sub.2 OC.sub.6 H.sub.5 blue                                        261 H CH.sub.3 SO.sub.2 OC.sub.6 H.sub.5 blue                                __________________________________________________________________________

                                      TABLE 14                                     __________________________________________________________________________       #STR249##                                                                       -                                                                           Ex. No.                                                                            E.sup.1                                                                          E.sup.2        E.sup.3        E.sup.4                                                                           E.sup.5                                                                            E.sup.6                                                                           E.sup.7                                                                            Hue on wool                  __________________________________________________________________________       262 H                                                                                                                            H H CH0##                                                                    .sub.3 H SO.sub.3 H                                                            bluish black                    - 263 H                                                                                                                         H H CH.sub.3 H H                                                             bluish black                    - 264 H CH.sub.3                                                                                                                H CH.sub.3 H SO.sub.3                                                        H bluish black                  - 265 H CH.sub.3                                                                                                                H CH.sub.3 H H dark                                                          blue                            - 266 H CH.sub.3                                                                                                                CH.sub.3 CH.sub.3 H                                                          SO.sub.3 H bluish black         - 267 Cl H SO.sub.2 O--C.sub.6 H.sub.5 CH.sub.3 OCH.sub.3 H SO.sub.3 H                                                        bluish black                   268 H H SO.sub.2 O--C.sub.6 H.sub.5 CH.sub.3 H CH.sub.3 SO.sub.3 H                                                             bluish black                    - 269 H                                                                                                                         H CH.sub.3 CH.sub.3 H                                                        H bluish black                  - 270 H H                                                                                                                       CH.sub.3 CH.sub.3 H H                                                        dark blue                       - 271 H                                                                                                                         H CH.sub.3 CH.sub.3 H                                                        H dark blue                  __________________________________________________________________________

                                      TABLE 15                                     __________________________________________________________________________       #STR258##                                                                       -                                                                           Ex. No.                                                                            E.sup.1                                                                          E.sup.2         E.sup.3    E.sup.4      Hue on wool                      __________________________________________________________________________       272 H                                                                                                                        H TR259##                                                                      blue 60##                         - 273 H CH.sub.3                                                                                                            CH.sub.2 C.sub.6 H.sub.5                                                     blue                                - 274 H                                                                                                                     H CH.sub.2 C.sub.6                                                           H.sub.5 blue                        - 275 H                                                                                                                     H CH.sub.2 C.sub.6                                                           H.sub.5 blue                        - 276 H CH.sub.3                                                                                                            #STR264##                                                                      blue 65##                         - 277 H H                                                                                                                   #STR266##                                                                      blue 67##                         - 278 Cl H                                                                                                                  #STR268##                                                                      blue 69##                         - 279 H H                                                                                                                   #STR270##                                                                      blue 71##                         - 280 H                                                                                                                     H TR272##                                                                      blue 73##                         - 281 H                                                                                                                     H C.sub.4 H.sub.9 blue                                                         - 282 H                                                                        H C.sub.3 H.sub.6                                                            OCH.sub.3 blue                   __________________________________________________________________________

                                      TABLE 16                                     __________________________________________________________________________       #STR276##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool                              __________________________________________________________________________       283 H                                                                                                                   H SO277##                                                                    .sub.3 H reddish blue                    - 284 CH.sub.3 CH.sub.3                                                                                                SO.sub.3 H reddish blue                                                        - 285 CH.sub.3 H                                                               H reddish blue                         - 286 H H                                                                                                              H reddish blue                         - 287 H H                                                                                                              H reddish blue                         - 288 H H                                                                                                              H reddish blue                         - 289 CH.sub.3                                                                                                         H H reddish blue                       - 290 H                                                                                                                H H reddish blue                       - 291 H                                                                                                                H H reddish blue                       - 292 H                                                                                                                H H reddish blue                       - 293 H                                                                                                                H H reddish blue                       - 294 H                                                                                                                H H reddish blue                    __________________________________________________________________________

                                      TABLE 17                                     __________________________________________________________________________       #STR289##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 Hue on wool                                      __________________________________________________________________________       295 H CH.sub.3                                                                                                     blue 90##                                   - 296 Cl H                                                                                                        blue 91##                                   - 297 H H                                                                                                         blue 92##                                   - 298 H H                                                                                                         blue 93##                                   - 299 H CH.sub.3                                                                                                  blue 94##                                   - 300 H H                                                                                                         blue 95##                                   - 301 H H                                                                                                         blue 96##                                   - 302 H H                                                                                                         blue 97##                                   - 303 H H                                                                                                         blue 98##                                   - 304 H H                                                                                                         blue 99##                                   - 305 H H                                                                                                         blue300##                                __________________________________________________________________________

                                      TABLE 18                                     __________________________________________________________________________       #STR301##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool                              __________________________________________________________________________       306 H NO.sub.2 H C.sub.4 H.sub.9 blue                                          307 H C.sub.6 H.sub.5 SO.sub.2 H C.sub.2 H.sub.5 blue                           - 308 H                                                                                                                               H C.sub.2                                                                    H.sub.5 blue                                                                     - 309 H                                                                        H C.sub.2                                                                    H.sub.5 blue                                                                     - 310                                                                          H (C.sub.2                                                                   H.sub.5).sub.2                                                                 N--SO.sub.2                                                                    C.sub.2 H.sub.5                                                                ,1 bluish ,1                                                                   black                     - 311                                                                                                                                 H (C.sub.2                                                                   H.sub.5).sub.2                                                                 N--SO.sub.2                                                                    C.sub.2 H.sub.5                                                                ,1 bluish ,1                                                                   black                     - 312 H CH.sub.2 ═CH--SO.sub.2 H C.sub.2 H.sub.5 blue                     313 H HOCH.sub.2 CH.sub.2 --SO.sub.2 H C.sub.2 H.sub.5 blue                    314 H CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 --SO.sub.2 H C.sub.2 H.sub.5                                                                 blue                     315 H ClCH.sub.2 CH.sub.2 --SO.sub.2 H CH.sub.3 blue                           316 H CH.sub.2 ═CH--SO.sub.2 H CH.sub.3 blue                                - 317                                                                                                                                 H H CH.sub.3                                                                 blue                      - 318 H                                                                                                                               H C.sub.2                                                                    H.sub.5 blue                                                                     - 319 H H                                                                      C.sub.2 H.sub.5                                                              blue                      - 320 H                                                                                                                               H C.sub.2                                                                    H.sub.5 blue                                                                     - 321 H                                                                        H C.sub.2                                                                    H.sub.5 blue                                                                     - 322 H C.sub.2                                                              H.sub.5 O.sub.2 C                                                              H C.sub.2 H.sub.5                                                              blue                     323 H                                                                                                                                  CSTR311##                                                                    .sub.2 H.sub.5                                                                 blue                      - 324 H                                                                                                                               C.sub.2 H.sub.5                                                              blue                      - 325 H                                                                                                                               C.sub.2 H.sub.5                                                              blue                     326                                                                                                                                    H SO314##                                                                    .sub.2 CH.sub.2                                                                CO.sub.2 H                                                                     CH.sub.3  ,1                                                                   bluish ,1 black                                                                  - 327                                                                          H SO.sub.2                                                                   CH.sub.2 CO.sub.2                                                              H C.sub.2 H.sub.5                                                               ,1 bluish ,1                                                                  black                     - 328                                                                                                                                 H SO.sub.2                                                                   CH.sub.2 CO.sub.2                                                              H CH.sub.3  ,1                                                                 bluish ,1 black                                                                  - 329                                                                          H SO.sub.2                                                                   CH.sub.2 CO.sub.2                                                              H CH.sub.3  ,1                                                                 bluish ,1 black                                                                  - 330 C.sub.6                                                                H.sub.5 --SO.sub.2                                                              H                                                                               CH.sub.3  ,1                                                                 bluish ,1 black                                                                  - 331 C.sub.6                                                                H.sub.5 --SO.sub.2                                                              H                                                                               C.sub.2 H.sub.5                                                               ,1 bluish ,1                                                                  black                     - 332                                                                                                                                 H TR320##                                                                      C.sub.2 H.sub.5                                                               ,1 bluish ,1                                                                  black                     - 333                                                                                                                                 H TR322##                                                                      CH.sub.3  ,1                                                                 bluish ,1 black                                                                  - 334 CO.sub.2                                                               CH.sub.3 H                                                                     CO.sub.2 CH.sub.3                                                              CH.sub.3 blue                                                                   335 CO.sub.2                                                                  CH.sub.3 H                                                                     CO.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                blue                     336 CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 blue                                                                 337 CO.sub.2                                                                  C.sub.2 H.sub.5 H                                                              CO.sub.2 C.sub.2                                                               H.sub.5 C.sub.2                                                                H.sub.5 blue                                                                    338 CO.sub.2                                                                  CH.sub.3 H                                                                     CO.sub.2 C.sub.3                                                               H.sub.7 CH.sub.3                                                               blue                     339 CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.6 H.sub.5 CH.sub.3 blue                 340 CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.6 H.sub.5 CH.sub.3 blue               __________________________________________________________________________

                                      TABLE 19                                     __________________________________________________________________________       #STR324##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 Hue on wool                                      __________________________________________________________________________     341  HO.sub.3 SOCH.sub.2 CH.sub.2                                                                   CH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                                                         reddish blue                          342 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 C.sub.6                                                       H.sub.5 reddish blue                  343 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 C.sub.6                                                     H.sub.5 reddish blue                  344 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3                                                   reddish blue                          345 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 (CH.sub.2).sub.3 OCH.sub.3                                                    reddish blue                          346 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3                                                       OCH.sub.2 C.sub.6 H.sub.5                                                      reddish blue                          347 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 C.sub.6 H.sub.5 reddish blue                                                    - 348 HO.sub.3 SOCH.sub.2                                                    CH.sub.2 CH.sub.3                                                                reddish blue                         - 349 HOCH.sub.2 CH.sub.2 CH.sub.3                                                                                       blue 26##                            - 350 H.sub.2 C═CH C.sub.2 H.sub.5                                                                                   blue 27##                            - 351 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                                blue 28##                            - 352                                                                                                                    CH.sub.3 CH.sub.2 C.sub.6                                                    H.sub.5 reddish blue                   - 353 HOC.sub.2 H.sub.4 CH.sub.3                                                                                         reddish blue                         - 354 HOC.sub.2 H.sub.4 C.sub.2 H.sub.5                                                                                  reddish blue                         - 355 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5                                                                                 reddish blue                         - 356 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 CO.sub.2 H                                                 reddish blue                        __________________________________________________________________________

                                      TABLE 20                                     __________________________________________________________________________       #STR333##                                                                       -                                                                           Ex.                                                                              No. E.sup.1 E.sup.2 E.sup.3 Hue on wool                                      __________________________________________________________________________     357    HO.sub.3 SOCH.sub.2 CH.sub.2                                                                        CH.sub.3                                                                             H      reddish blue                            358 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 H reddish blue                                                        359 HO.sub.3 SOCH.sub.2                                                       CH.sub.2 C.sub.3 H.sub.7 H                                                     reddish blue                             - 360                                                                                                                  CH.sub.3 H reddish blue                                                        - 361                                                                          C.sub.2 H.sub.5 H reddish blue         - 362                                                                                                                  CH.sub.3 H reddish blue                                                        - 363                                                                          C.sub.2 H.sub.5 H reddish blue         - 364 HO.sub.2 CCH.sub.2 CH.sub.3 H reddish blue                              365 (HOCH.sub.2 CH.sub.2).sub.2 N CH.sub.3 H reddish blue                      366 HOCH.sub.2 CH.sub.2 NH CH.sub.3 H reddish blue                             367 HOCH.sub.2 CH.sub.2 NH C.sub.2 H.sub.5 H reddish blue                      368 HO.sub.2 CCH.sub.2 NH C.sub.2 H.sub.5 H reddish blue                       369 HO.sub.2 CCH.sub.2 CH.sub.2 NH CH.sub.3 H reddish blue                     370 HO.sub.2 CCH.sub.2 CH.sub.2 NH C.sub.2 H.sub.5 H reddish blue                                                      371 HO.sub.3 SOCH.sub.2                                                       CH.sub.2 CH.sub.3 CH.sub.3                                                     reddish blue                          __________________________________________________________________________

                                      TABLE 21                                     __________________________________________________________________________       #STR338##                                                                       -                                                                           Ex. No.                                                                            E.sup.1         E.sup.2                                                                           E.sup.3      E.sup.4  E.sup.5                                                                           Hue on wool                    __________________________________________________________________________       372 HO.sub.2 CCH.sub.2 CH.sub.3                                                                                                H SO.sub.3 H bluish                                                          black                             - 372 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5                                                                                      H SO.sub.3 H bluish                                                          black                             - 374 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                                     H SO.sub.3 H bluish                                                          black                             - 375 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3                                                                                   H H blue                        - 376 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                            H H blue                        - 377 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3                                                                                   H H reddish blue                                                               - 378 HO.sub.3 SOCH.sub.                                                     2 CH.sub.2 C.sub.2                                                             H.sub.5                                                                          H H reddish blue                                                               - 379 HO.sub.3 SOCH.sub.                                                     2 CH.sub.2 C.sub.2                                                             H.sub.5                                                                          SO.sub.2 N(C.sub.2                                                           H.sub.4 OCH.sub.3).sub.2                                                       H reddish blue                    - 380 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 COC.sub.6 H.sub.5 H                                                      H reddish blue                   381 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 COC.sub.6 H.sub.5 Cl H                                                      reddish blue                     382 CH.sub.2 ═CH CH.sub.3 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H                                                          bluish black                     383 CH.sub.2 ═CH C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 H                                                              SO.sub.3 H bluish black                                                          - 384                                                                          C.sub.2 H.sub.5                                                              SO.sub.2 C.sub.6 H.sub.5                                                       H H blue                          - 385 (HOC.sub.2 H.sub.4).sub.2 N CH.sub.3                                                                                    H SO.sub.3 H bluish                                                          black                             - 386 CH.sub.2 ═CHCH.sub.2 CH.sub.3                                                                                       H SO.sub.3 H bluish                                                          black                             - 387 CH.sub.2 ═CHCH.sub.2 C.sub.2 H.sub.5                                                                                H SO.sub.3 H bluish                                                          black                             - 388 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 C.sub.6                                                         H.sub.5 H H blue                 389 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.2                                                           CH.sub.2 C.sub.6 H.sub.5                                                       H H blue                         390 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.2                                                           CH.sub.2 OC.sub.6 H.sub.5                                                      H H blue                         391 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 H H                                                       blue                              - 392                                                                                                                         C.sub.2 H.sub.5                                                                H H reddish blue             __________________________________________________________________________

                                      TABLE 22                                     __________________________________________________________________________       #STR353##                                                                       -                                                                           Ex. No. E.sup.1      E.sup.2                                                                              E.sup.3          Y    Hue on wool                   __________________________________________________________________________     393     HOCH.sub.2 CH.sub.2 NH                                                                      CH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                                                        CO   blue                            394 (HOCH.sub.2 CH.sub.2).sub.2 N CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CO                                                        blue                             - 395                                                                                                                          CH.sub.3                                                                       CO blue #                      - 396                                                                                                                          C.sub.2 H.sub.5                                                                CO blue #                      - 397 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                                      CO blue #                      - 398 CH.sub.2 ═CHCH.sub.2 C.sub.2 H.sub.5                                                                                 CO blue #                      - 399 CH.sub.2 ═CHCH.sub.2 C.sub.2 H.sub.5                                                                                 CH.sub.2 blue                  - 400 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3                                                       CH.sub.2 blue                  401 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2                                                            CH.sub.2 OCH.sub.2                                                             C.sub.6 H.sub.5 CH.sub.2                                                       blue                            402 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CO                                                           blue                            403 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 C.sub.6                                                             H.sub.5 CO blue                 404 HO.sub.2 CCH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CO                                                          blue                             - 405 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5                                                                                       CH.sub.2 blue                  - 406 HO.sub.2 CCH.sub.2 CH.sub.3                                                                                              CH.sub.2 blue                  - 407 HO.sub.2 CCH.sub.2 CH.sub.3                                                                                              CO blue #                      - 408 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5                                                                                       CO blue #                      - 409                                                                                                                          CH.sub.3                                                                       CO blue #                      - 410 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                                      CO blue #                      - 411 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5                                                                                      CH.sub.2 blue                  - 412 H.sub.2 C═CH C.sub.2 H.sub.5                                                                                         CH.sub.2 blue               __________________________________________________________________________

EXAMPLE 413

a) 16.9 g of the diazo component of formula ##STR370## were dissolved in 30 ml of water at pH 3.5 using 5.9 g of sodium bicarbonate, and the solution was then cooled down with ice to 0° C. and admixed with 12.6 ml of 36% strength hydrochloric acid. The suspension was then diazotized with 18.3 ml of 3.33 N aqueous sodium nitrite solution. The resulting diazonium salt mixture was mixed with a freshly precipitated suspension of 20.5 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid monosodium salt (pH about 1) after excess nitrous acid had been destroyed. The mixture was coupled overnight to obtain a suspension of the red dye of the formula ##STR371## b) The suspension obtained was adjusted to pH 10 at room temperature and the resulting solution was stirred at pH 10 for 3.5 h. The pH was then adjusted to 7, 0.06 mol of the conventionally prepared diazonium salt of diethyl 2-aminoterephthalate was added in the form of a solution, and the mixture was subsequently stirred for 3 h at pH 6-7. The resulting blue dye was precipitated with sodium chloride at pH 6-6.5 and isolated in a conventional manner.

Drying left 50 g of the dye of the formula ##STR372## which still comprised a total of 16 g of sodium chloride and water of crystallization. The dye forms a blue solution in water with absorption maxima in the visible region at 396 and 582 nm and a shoulder at 625 nm.

Dark blue to bluish black dyeings are obtained on wool according to the customary dyeing methods for anionic wool dyes. The buildup capacity and also the wet- and lightfastness properties on wool are excellent.

EXAMPLE 414

The dye described in Example 413 a) as a suspension was neutralized. Then 0.06 mol of the diazonium salt solution of diethyl 2-aminoterephthalate was added while the pH of the coupling solution was maintained at from 5.5 to 7.0 using sodium bicarbonate. The ready-prepared coupling mixture was spray-dried at pH 6.5, affording the dye of the formula ##STR373## as a bluish black powder (together with the salts formed in the course of the reaction) in the form of the sodium salt. The powder forms a blue solution in water (λ_(max) in water: 397 and 585 nm, shoulder at 626 nm) and dyes wool according to the dyeing processes customary for wool dyes (acetic acid to formic acid medium) in a blue to bluish black shade having excellent light- and wetfastness properties.

EXAMPLE 415

a) The dye described in 413 a) as a suspension was neutralized.

Then 0.06 mol of the diazonium salt of 4-aminodiphenyl sulfone (diazotized in water in a conventional manner with hydrochloric acid and sodium nitrite) was added and the pH of the coupling mixture was maintained at 5-7. The mixture was subsequently stirred for 1 h at pH 6.5 and thereafter spray-dried, affording a black powder comprising 51 g of the dye of the formula ##STR374## in the form of the sodium salt (λ_(max) in water: 600 nm, at pH 4-6). The dye dyes wool in a deep bluish black shade having excellent wetfastness properties and good lightfastness.

b) However, on adjusting the blue reaction solution to pH 10 and subsequently stirring it at room temperature for 4 h, the resulting novel dye of the formula ##STR375## was readily precipitated with sodium chloride at pH 6.5. This dye dyes wool according to the customary dyeing processes (acetic-formic acid medium) in a dark blue to black shade having excellent wetfastness properties, similarly to the dye described under a). Blue dyeings are obtained on leather (λ_(max) in water: at pH ˜4 to 5: 392 and 596 nm)

EXAMPLE 416

The dye described in Example 413 a) as a suspension was neutralized at room temperature. Then 0.06 mol of the diazonium salt of the formula ##STR376## was added in the form of an aqueous solution and the pH of the coupling reaction was held within the range from 5.5 to 7.5 using sodium bicarbonate, affording a solution of the dye of the formula ##STR377##

Spray drying at a pH from about 6 to 6.5 gave a black powder which forms a blue solution in water. The absorption spectrum in the visible region had maxima at 394 nm and 584 nm and also a shoulder at about 620 nm.

Adjusting the dye solution to pH 10 and stirring at room temperature for 4 h yielded the novel dye of the formula ##STR378## (λ_(max) in water at pH 4-6: 581 nm, shoulder at about 618 nm). This dye could be precipitated with sodium chloride at pH 6-7.5 and isolated in a conventional manner.

Both dyes dye wool in a dark blue to navy shade having excellent wet- and lightfastness properties. The exhaustion capacity is good.

EXAMPLE 417

a) 29.6 g of the diazo component of the formula ##STR379## were dissolved using 72 ml of 18.5% strength by weight hydrochloric acid. Ice was added, followed at 0-7° C. by 37.5 ml of 23% strength aqueous sodium nitrite solution. The mixture was subsequently stirred at 0-7° C. for 30 min, excess nitrous acid was destroyed, and then 46 g of an aqueous solution, adjusted to pH 6, of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid were added dropwise over 1.5 h with very thorough stirring, and the mixture was subsequently stirred overnight, affording the red dye of the formula ##STR380## as a thick suspension. The dye gives a red solution in water and has an absorption maximum at 518 nm in the visible spectrum.

b) Then a diazonium salt solution was added, which had been prepared as follows: 17.7 g of the diazo component of the formula ##STR381## were diazotized with water, dilute hydrochloric acid and sodium nitrite and also a little glacial acetic acid in a conventional manner at from 10 to 20° C. The reaction mixture was neutralized with dilute sodium hydroxide solution, affording the dye of the formula ##STR382## which was precipitated with sodium chloride and then isolated in a conventional manner. The black powder dissolves in water with a reddish blue color (λ_(max) : 570 nm, shoulder at 625 nm) and dyes wool (acetic- to formic-acid medium) in a deep reddish blue shade having very good lightfastness.

The dyes listed in the table which follows are obtained in a similar manner.

    TABLE 23        -       ##STR383##      Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 E.sup.6 Hue on wool        418 H C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H CO.sub.2 CH.sub.3 H CO.sub.2        CH.sub.2       CH.sub.3 reddish blue               419 H       ##STR384##       SO.sub.3 H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue      420 H       ##STR385##       H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2       CH.sub.3 reddish blue                                              421 CH.sub.3       ##STR386##       CH.sub.3 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue      422 H       ##STR387##       H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2       CH.sub.3 reddish blue                                              423 H       ##STR388##       H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue      424 H       ##STR389##       H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2       CH.sub.3 reddish blue                                              425 H       ##STR390##       H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2       CH.sub.3 reddish blue                                              426 H       ##STR391##       H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 blue                                     427 H       ##STR392##       H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2       H.sub.5 blue                                                    428 H C.sub.6 H.sub.5      OSO.sub.2 H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 blue                    429 H C.sub.6 H.sub.5 OSO.sub.2 H      CO.sub.2 C.sub.3 H.sub.7 H CO.sub.2       CH.sub.3 blue                         430 H C.sub.6 H.sub.5 OSO.sub.2 H        CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.3       H.sub.7 blue                                            431 H       ##STR393##       H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 blue                                     432 CH.sub.3       ##STR394##       H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 blue                                     433 H       ##STR395##       H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 reddish blue                                     434 C.sub.6 H.sub.5 SO.sub.2 H H CO.sub.2        CH.sub.3 H CO.sub.2       CH.sub.3 blue                                       435 C.sub.6 H.sub.5        SO.sub.2 SO.sub.3 H H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue             436 C.sub.6 H.sub.5 SO.sub.2 H SO.sub.3 H CO.sub.2 CH.sub.3 H      CO.sub.2       CH.sub.3 dark blue                                               437      C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H H CO.sub.2 C.sub.2 H.sub.5 H      CO.sub.2 C.sub.2       H.sub.5 dark blue                      438       ##STR396##       SO.sub.3 H H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 dark blue                                                439       ##STR397##       H H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 dark blue                                                                         440       ##STR398##       H H CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3 dark blue                                       441 C.sub.6 H.sub.5 CO Cl H CO.sub.2      CH.sub.3 H CO.sub.2       CH.sub.3 blue                         442 CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3                                                       ##STR399##       SO.sub.3       H H reddish blue              443 CO.sub.2 CH.sub.3 H CO.sub.2       CH.sub.3                                                       ##STR400##       H H reddish blue      444 CO.sub.3 CH.sub.3 H CO.sub.2       CH.sub.3                                                       ##STR401##       H H reddish blue      445 H       ##STR402##       H       ##STR403##       H H reddish blue      446 H (CH.sub.3).sub.2       N--SO.sub.2 H                                                       ##STR404##       H H reddish blue      447 H       ##STR405##       H       ##STR406##       SO.sub.3       H H navy              448 CH.sub.3       ##STR407##       H       ##STR408##       SO.sub.3       H H navy              449 H (C.sub.2 H.sub.5).sub.2       N--SO.sub.2 H                                                       ##STR409##       H SO.sub.3       H navy                 450 H       ##STR410##       H       ##STR411##       H H blue      451 H       ##STR412##       H       ##STR413##       H H reddish blue      452 H C.sub.6 H.sub.5       OSO.sub.2 H                                                       ##STR414##       H H reddish blue      453 H CH.sub.2       ═CHSO.sub.2 H                                                       ##STR415##       H H navy      454 H CH.sub.2       ═CHSO.sub.2 H                                                       ##STR416##       H H navy      455 H CH.sub.2 ═CHCH.sub.2       SO.sub.2 H                                                       ##STR417##       H H navy      456 H CH.sub.2       ═CHSO.sub.2 H                                                       ##STR418##       H H navy      457 H CH.sub.2       ═CHSO.sub.2 H                                                       ##STR419##       H H navy      458 H C.sub.6 H.sub.5       SO.sub.2 H                                                       ##STR420##       H H reddish blue      459 H C.sub.6 H.sub.5       SO.sub.2 H                                                       ##STR421##       H H reddish blue      460 H C.sub.6 H.sub.5 SO.sub.2 SO.sub.3       H                                                       ##STR422##       H H reddish blue      461 H       ##STR423##       H       ##STR424##       H H reddish blue      462       ##STR425##       H H       ##STR426##       H H reddish blue      463       ##STR427##       H H       ##STR428##       H H reddish blue      464 CH.sub.3 HO.sub.3 SOCH.sub.2 CH.sub.2       SO.sub.2 CH.sub.3                                                       ##STR429##       H H navy      465 H CH.sub.3 O.sub.2       C H                                                       ##STR430##       SO.sub.3       H H reddish blue              466 H       ##STR431##       H       ##STR432##       SO.sub.3       H H reddish blue              467 SO.sub.3 H (C.sub.2 H.sub.5).sub.2       NSO.sub.2 H                                                       ##STR433##       H H reddish blue      468 SO.sub.3       H                                                       ##STR434##       H       ##STR435##       H H reddish blue

EXAMPLE 469

225 g of 1-aminonaphthalene-3-sulfonic acid were dissolved in 800 ml of water at pH 7 (sodium hydroxide solution) and 50° C. 258 g of 4-acetaminobenzenesulfonyl chloride were then added a little at a time with very thorough stirring while the pH of the mixture was maintained within the range from 6.0 to 7.2 by the simultaneous addition of 60 g of sodium carbonate. The mixture was subsequently stirred at pH 7 for 1 hour, then adjusted to pH 9 with sodium hydroxide solution and admixed with 160 g of dimethyl sulfate added dropwise over 15 min while the reaction pH was maintained at >8 to 9 using sodium hydroxide solution. The resulting suspension was subsequently stirred at 45-50° C. for 2 h, then 100 ml of 25% strength by weight aqueous ammonia solution were added, and the dye was precipitated with 250 g of sodium chloride and filtered off with suction. The filter residue was taken up with 300 ml of methanol and 500 ml of water, the mixture was admixed with 135 g of concentrated sulfuric acid and stirred for 6 h under evaporative cooling. Methanol was then distilled off with a little water, the suspension was stirred overnight until cold, the precipitate was isolated on a suction filter, washed with a little ice-cold, highly dilute hydrochloric acid and dried to leave 350 g of the diazo component of the formula ##STR436##

The H--NMR spectrum recorded in hexadeuterodimethyl sulfoxide showed the --N--CH₃ signal at 3.18 ppm (singlet of the CH₃ protons).

EXAMPLE 470

225 g of 1-aminonaphthalene-3-sulfonic acid were reacted with 258 g of 4-acetaminosulfonyl chloride similarly to Example 469 and alkylated with dimethyl sulfate, and then excess dimethyl sulfate was destroyed with ammonia. Sodium hydroxide solution was then used to render the reaction mixture strongly alkaline (pH >12 to about 13), and the mixture was stirred at 80 to 100° C. for 5 h while the pH was held at >12. Thereafter it was slowly acidified with hydrochloric acid to a pH of about 1 to 1.5 and cooled down to room temperature. After stirring overnight the resulting suspension was filtered off with suction and washed once with very dilute hydrochloric acid, affording the diazo component of the formula ##STR437## in similar yield and comparable purity.

The following compounds are obtained in a similar manner:

    __________________________________________________________________________     Ex. No.                       E                                                __________________________________________________________________________       471  472                                                                                                     CHTR438##                                                                    .sub.3 (S., 3.14 ppm) and  C.sub.2 H.sub.5                                       - 473  474                                                                     CH.sub.3 (S., 3.18 ppm)  C.sub.2 H.sub.5                                       - 475  476                                                                     CH.sub.3 (S., 3.06 ppm)  C.sub.2 H.sub.5                                       - 477  478                                                                     CH.sub.3  C.sub.2 H.sub.5                         - 479                                                                                                       singlet at 3.05 ppm                            __________________________________________________________________________

EXAMPLE 480

250 g of N-ethylaminobenzene-4-sulfonic acid were stirred together with 800 ml of water and adjusted to pH 7 at 50-55° C. using sodium hydroxide solution. Then 306 g of 4-acetaminobenzenesulfonyl chloride were added a little at a time with vigorous stirring while the reaction mixture pH was maintained within the range from 6 to 7.5 using sodium carbonate. The mixture was subsequently stirred for 1 h, then adjusted to pH 12.5-14 and subsequently stirred under evaporative cooling at a pH >12.5 to 13 for 7 h during which further sodium hydroxide solution was added. The mixture was then acidified with hydrochloric acid at pH 1 and 70° C., cooled down to room temperature and allowed to crystallize overnight. The precipitated product was filtered off with suction and washed with cold dilute hydrochloric acid. Drying left 400 g of the diazo component of the formula ##STR443##

The H--NMR spectrum of the product shows the protons of the C₂ H₅ group as a quartet at 3.51 ppm (quartet of the --CH₂ -- group) 0.9 ppm (triplet of the --CH₃ -- group) recorded in dimethyl sulfoxide.

Favorable results are also obtained with the following dyes:

    __________________________________________________________________________     Dye                                                                              No.                                                                          __________________________________________________________________________       F1                                                                                                                                       navy                                                                         .sub.max :  587                                                                nm                      - F2                                                                                                                                    .sub.max :                                                                   598 nm                  - F3                                                                                                                                    navy                                                                         .sub.max :  600                                                                nm                      - F4                                                                                                                                    .sub.max :                                                                   596.5 nm                                                                         - F5                                                                           greenish                                                                     blue                    - F6                                                                                                                                    .sub.max :                                                                   584 nm                  - F7                                                                                                                                    .sub.max :                                                                   587 nm                                                                         shoulder:  620                                                                 nm                      - F8                                                                                                                                    .sub.max :                                                                   584 nm                                                                         shoulder:                                                                      ˜615 nm                                                                    - F9                                                                           navy                                                                         .sub.max :  600                                                                nm                      - F10                                                                                                                                   .sub.max :                                                                   584 nm                  - F11                                                                                                                                   .sub.max :                                                                   596 nm                  - F12                                                                                                                                   .sub.max :                                                                   598 nm                  - F13                                                                                                                                   .sub.max :                                                                   597 nm                  - F14                                                                                                                                   .sub.max :                                                                   594 nm                  - F15                                                                                                                                   navy 58##             - F16                                                                                                                                   bluish  black         - F17                                                                                                                                   .sub.max :                                                                   596 nm                  - F18                                                                                                                                   navy                                                                         .sub.max :  598                                                                nm                      - F19                                                                                                                                   .sub.max :                                                                   597 nm                  - F20                                                                                                                                   navy 63##             - F21                                                                                                                                   .sub.max :                                                                   581 nm                                                                         shoulder                                                                       ˜618 nm                                                                    - F22                                                                          .sub.max :                                                                   583 nm                                                                         shoulder  at                                                                   620 nm                  - F23                                                                                                                                   .sub.max :                                                                   582 nm                                                                         shoulder  625                                                                  nm                      - F24                                                                                                                                   .sub.max :                                                                   599 nm                  - F25                                                                                                                                   .sub.max :                                                                   582 nm                  - F26                                                                                                                                   .sub.max :                                                                   594 nm                  - F27                                                                                                                                   .sub.max :                                                                   597 nm                  - F28                                                                                                                                   .sub.max :                                                                   595 nm                  - F29                                                                                                                                   .sub.max :                                                                   594 nm                  - F30                                                                                                                                   navy 73##             - F31                                                                                                                                   dark blue                                                                      - F32                                                                          navy                                                                         .sub.max :  580                                                                nm                      - F33                                                                                                                                   dark blue                                                                    .sub.max :  579                                                                nm  401 nm                                                                     shoulder  622                                                                  nm                      - F34                                                                                                                                   .sub.max :                                                                   572 nm                                                                         shoulder                                                                       ˜625 nm                                                                  reddish  blue                                                                    - F35                                                                          .sub.max :                                                                   395 nm  582 nm                                                                 shoulder  623                                                                  nm                      - F36                                                                                                                                   bluish  black         - F37                                                                                                                                   .sub.max :                                                                   402 nm  574 nm                                                                 navy  shoulder                                                                 ˜625 nm                                                                    - F38                                                                          navy 81##             - F39                                                                                                                                   navy 82##             - F40                                                                                                                                   dark blue                                                                      - F41                                                                          dark blue                                                                      - F42                                                                          reddish  blue         - F43                                                                                                                                   reddish  blue         - F44                                                                                                                                   navy 87##             - F45                                                                                                                                   navy 88##             - F46                                                                                                                                   navy 89##             - F47                                                                                                                                   .sub.max :                                                                   576 nm                                                                         shoulder  615                                                                  nm                      - F48                                                                                                                                   .sub.max :                                                                   585 nm                                                                         shoulder                                                                       ˜620 nm                                                                    - F49                                                                          .sub.max :                                                                   576 nm                                                                         shoulder                                                                       ˜615 nm                                                                    - F50                                                                          .sub.max :                                                                   594 nm                  - F51                                                                                                                                   .sub.max :                                                                   594 nm                  - F52                                                                                                                                   .sub.max :                                                                   599 nm                  - F53                                                                                                                                   .sub.max :                                                                   599 nm                  - F54                                                                                                                                   dark blue                                                                      - F55                                                                          navy 98##             - F56                                                                                                                                   navy 99##             - F57                                                                                                                                   .sub.max :                                                                   596 nm                  - F58                                                                                                                                   .sub.max :                                                                   597 nm                  - F59                                                                                                                                   .sub.max :                                                                   600 nm                  - F60                                                                                                                                   .sub.max :                                                                   574 nm                                                                         shoulder                                                                       ˜615 nm                                                                    - F61                                                                          .sub.max :                                                                   598 nm                  - F62                                                                                                                                   .sub.max :                                                                   598 nm                  - F63                                                                                                                                   .sub.max :                                                                   598 nm                  - F64                                                                                                                                   .sub.max :                                                                   598 nm                  - F65                                                                                                                                   .sub.max :                                                                   575 nm  navy                                                                     - F66                                                                          .sub.max :                                                                   584 nm                                                                         shoulder  620                                                                  nm                      - F67                                                                                                                                   .sub.max :                                                                   583 nm                                                                         shoulder  625                                                                  nm                      - F68                                                                                                                                   .sub.max :                                                                   583 nm                                                                         shoulder  625                                                                  nm                      - F69                                                                                                                                   .sub.max :                                                                   615 nm                  - F70                                                                                                                                   .sub.max :                                                                   615 nm                  - F71                                                                                                                                   .sub.max :                                                                   584 nm                                                                         shoulder                                                                       ˜625 nm                                                                    - F72                                                                          reddish  blue         - F73                                                                                                                                   dark blue                                                                      - F74                                                                          dark blue                                                                      - F75                                                                          navy 18##             - F76                                                                                                                                   navy 19##             - F77                                                                                                                                   navy 20##             - F78                                                                                                                                   .sub.max :                                                                   575 nm  (400                                                                   nm)  shoulder                                                                  620 nm  navy                                                                     - F79                                                                          .sub.max :                                                                   581 nm  (397                                                                   nm)  shoulder                                                                  620 nm                  - F80                                                                                                                                   .sub.max :                                                                   591 nm  (405                                                                   nm)  shoulder                                                                  638 nm                  - F81                                                                                                                                   navy 24##             - F82                                                                                                                                   reddish  navy                                                                 .sub.max :                                                                    560 nm  (405                                                                   nm)  shoulder:                                                                 about  605 nm                                                                    - F83                                                                          navy 26##             - F84                                                                                                                                   navy 27##             - F85                                                                                                                                   navy 28##             - F86                                                                                                                                   navy 29##             - F87                                                                                                                                   navy 30##             - F88                                                                                                                                   navy 31##             - F89                                                                                                                                   navy 32##             - F90                                                                                                                                   navy533##          __________________________________________________________________________ 

What is claimed is:
 1. A Disazo dye of the formula III ##STR534## where one of the two radicals X¹ and X² is hydroxyl and the other is amino,R^(1') is a radical of the formula CO--OAlk, CO--OAr, SO₂ --Ar, SO₂ --OAr, ##STR535## R² is hydrogen or R² and R^(1') together are a radical of the formula

    O--NZ'--CO

    or ##STR536## R.sup.3 is hydrogen, hydroxysulfonyl, C.sub.1 -C.sub.4 -alkyl, halogen or a radical of the formula SO.sub.2 --OAr, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr or R.sup.3 and R.sup.2 together are a radical of the formula CO--NZ.sup.1 --Y,

R⁴ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAlk, CO--NHAr, CO--N(Ar)Alk, CO--N(Alk)₂, SO₂ --Alk, SO₂ --OAr, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk or SO₂ --NHAr, R⁵ is hydrogen, C₁ -C₄ -alkyl, halogen or hydroxysulfonyl, and R¹⁰ is SO₂ --CH₂ CH═CH₂. SO₂ --CH═CH₂ or SO₂ --C₂ H₄ --Q and R¹⁰ is in the 3- or 4-position, and Alk is C₁ -C₈ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfate, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenoxy, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl, Ar is phenyl or naphthyl, and each of these radicals may be substituted by C₁ -C₄ -alkyl, phenyl-(C₁ -C₄)-alkyl, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-(C₁ -C₄)-alkyl, phenoxy, hydroxy, carboxyl, C₁ -C₄ -alkanoylamino with or without interruption by 1 oxygen atom in ether function in the alkyl chain, benzoylamino, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO₂ --Alk, SO₂ --CH₂ CH═CH₂, SO₂ --CH═CH₂, SO2--C₂ H₄ --Q, SO₂ --NHAlk, SO₂ --N(alk)₂, SO₂ --G, SO₂ --OG, SO₂ --NHG or SO₂ --N(Alk)G, Y is methylene or carbonyl, Z¹ is hydrogen or a radical of the formula Alk or Ar, Z² is hydrogen or hydroxysulfonyl, Q is hydroxyl or an alkali-detachable group, and G is phenyl which may be substituted by C₁ -C₄ -alkyl, carboxyl, hydroxysulfonyl or C₁ -C₄ -alkanoylamino or is naphthyl which may be substituted by hydroxysulfonyl.
 2. The Disazo dye as claimed in claim 1, wherein R¹⁰ is a radical of the formula SO₂ --C₂ H₄ --Q¹ where Q¹ is an alkali-detachable group.
 3. The Disazo dye as claimed in claim 1, wherein R¹, is an oxadiazole radical.
 4. The Disazo dye of the formula I ##STR537## where one of the two radicals X¹ and X² is hydroxyl and the other is amino,R¹ is hydrogen, hydroxysulfonyl or a radical of the formula CO--Ar, CO--OAlk, CO--OAr, SO₂ --Ar, SO₂ --Alk, SO₂ --OAr, ##STR538## R² is hydrogen or R² and R¹ together are a radical of the formula

    O--NZ.sup.1 --CO

    or ##STR539## R.sup.3 is hydrogen, hydroxysulfonyl, C.sub.1 -C.sub.4 -alkyl, halogen or a radical of the formula SO.sub.2 --OAr, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr or R.sup.3 and R.sup.2 together are a radical of the formula CO--NZ1--Y,

R⁴ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAlk, CO--NHAr, CO--N(Ar)Alk, CO--N(Alk)₂, SO₂ --Alk, SO₂ --OAr, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk or SO₂ --NHAr, R⁵ is hydrogen, C₁ -C₄ -alkyl, halogen or hydroxysulfonyl, and R⁶, R⁷ and R⁸ are each independently of the others hydrogen, C₁ -C₄ -alkyl, halogen, cyano, nitro, hydroxysulfonyl or a radical of the formula CO--Ar, CO--OAr, CO--OAlk, CO--N(Ar)Alk, CO--N(Alk)₂, SO₂ --Ar, SO₂ --Alk, SO₂ --CH₂ CH═CH₂, SO₂ --CH═CH₂, SO₂ --C₂ H₄ --Q, SO₂ --OAr, ##STR540## where Alk is C₁ --C₈ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfate, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenoxy, phenyl or hydroxysulfonylphenyl, or is C₅ -C₈ -cycloalkyl, Ar is phenyl or naphthyl, and each of these radicals may be substituted by C₁ -C₄ -alkyl, phenyl-(C₁ -C₄)-alkyl, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-(C₁ -C₄)-alkyl, phenoxy, hydroxy, carboxyl, C₁ -C₄ -alkanoylamino with or without interruption by 1 oxygen atom in ether function in the alkyl chain, benzoylamino, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO₂ --Alk, SO₂ --CH₂ CH═CH₂, SO₂ --CH═CH₂, SO2--C₂ H₄ --Q, SO₂ --NHAlk, SO₂ --N(alk)₂, SO₂ --G, SO₂ --OG, SO₂ --NHG or SO₂ --N(Alk)G, Y is methylene or carbonyl, Z¹ is hydrogen or a radical of the formula Alk or Ar, Z² is hydrogen or hydroxysulfonyl, Q is hydroxyl or an alkali-detachable group, and G is phenyl which may be substituted by C₁ -C₄ -alkyl, carboxyl, hydroxysulfonyl or C₁ -C₄ -alkanoylamino or is naphthyl which may be substituted by hydroxysulfonyl, and one of the radicals R⁷ or R⁸ is a radical of the formula SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --N(Ar)Alk, SO₂ --NHAr or pyrrolidinylsulfonyl, piperidinylsulfonyl or morpholinylsulfonyl and the other radical and the radical R⁶ are each hydrogen or R³ is a radical of the formula SO₂ --N(Ar)Alk and the radicals R¹, R², R⁴ and R⁵ are each hydrogen.
 5. The Disazo dye as claimed in claim 4 containing a radical of the formula SO₂ --C₂ H₄ --Q¹ where Q¹ is an alkali-detachable group.
 6. The Disazo dye as claimed in claim 4, wherein R³ and/or R⁷ are each a radical of the formula SO₂ --N(Ar)Alk.
 7. The Disazo dye as claimed in claim 4, wherein R³ and/or R⁷ are each a radical of the formula SO₂ --N(Ar)Alk where Ar contains a radical of the formula SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂ or SO₂ --CH₂ --CH═CH₂.
 8. The Disazo dye as claimed in claim 4, wherein R¹, R⁶, R⁷ or R⁸ is an oxadiazole radical.
 9. A Disazo dye of the formula IV ##STR541## where R¹, R², R³, R⁴, R⁵, X¹, X², Alk and Ar are each as defined in claim 4 and the sulfonamide radical is in the 3- or 4-position.
 10. A method of dyeing wool at a pH from 3 to 7, which comprises applying thereto a disazo dye as claimed in claim
 2. 11. A method of dyeing wool at a pH from 3 to 7, which comprises applying thereto a disazo dye as claimed in claim
 5. 12. A method of dyeing a natural or synthetic substrates which comprises applying thereto a disazo dye as claimed in claim
 1. 13. A method of dyeing a natural or synthetic substrates which comprises applying thereto a disazo dye as claimed in claim
 4. 